Couplers for color photography



. 2,920,961 coUP Rs-Fo COLOR ,PHOTQGRAPHY waltenM. Bush and JohmR. Thirtle, Rochester, N;Y., assigntn-s. to. Eastman. Kodak: Company Rochester,

N.Y.,'a corporation of New Jersey No Drawing. ApplicationJuly 29, 1957 Serial No. 674,5 72

1 Claim. (CL. 96-400).

following general formula:

where A represents a functional group linking the n:v alkylcyclohexyloxyalkylene substituent to the coupler- .12.-v represents a hydrogen atom or an alkyl group of from. 1 to 4 carbon atoms, R represents: a.hyd roge n atom and, R represents an n-alkyl group ofat least 5 carbon atoms. or both R and R? represent such n-alkyl groups and n:. represents a positive integer of from 1 to 4. The n-alkyl -r cyclohexyloxyalkylene group is necessarily linked were coupler molecule in a non-coupling position.

A unique feature of the described n-alkylcyclohexyloxy substituted couplers of the invention lies in the fact that the alkyl groups R and R must be n-alkyl groups because secondary or tertiary alkylcyclohexyloxy substituted couplersdo not appear to be capable. ofsynthesis; This is based upon the fact that duringthe hydrogenation" step shown in the synthesis hereafter, a cleavage takes placeat the oxygen atom of the alkylcyclohexyloxy group either a secondary alkylcyclohexyl or tertiary allgyloyclosv hexyl groupv is attached to the oxygen atom.

A further unique and advantageous characterisiis: of the. n-alkylcyclohexyloxy substituted couplers of the invention lies in the fact that the couplers have much lower melting points than the analogousv alkylphenoxy couplers. Eor example, coupler VII below melts at a temperature4 1 C. below the melting point of the analogous alkylphenorry coupler. This property greatly facilitates the incorpora tion of'the couplers into photographic emulsions by means of coupler solvents. That is, the couplers may be dis persed in a coupler solvent for incorporationinto emulsions at about 40 0. lower temperature which avoids. degradation of the coupler. V

The following are representative oi the n-alkyleycle United States Patent-C ce Patented Jan. 12, 1960 ylpxy u s tut d couplers. sqntemnla db rheumtionz $-[a-(3-n-pentadecylcyclohexyloxy)acetamido] 2,4 dlchloro- 3-methylpheno1 r9xy-2[M2,4-diruamy y g e yl xy).: hutyllnaphh- (III) v H H;

1-(2,4,6-trichlorophenyl)-3-[3a-(2,4 d1 n amylcyclohexyloxy)-acetamido]benzamldo-fi-pyrazolone oxy)-acetamldo]ben2arnido-5 pyrazo1one W )v methoxyacetaniltde 11-{3-[7 (4 n amylcyclohexyloxy)butyramido1benzoyl} 2- (v11) viscous oil, distilling at 235-255 and 0.1 mm. An-

alysis.Calculated for C N Cl NO C, 63.4; H, 8.3; QNHCOOHNOQ 01, 15.0; N, 3.0. Found: 0, 63.8; H, 8.6; 01, 14.5; N, 3.1. CH: 6 The analogous diamylphenoxy compound prepared in Ha Hz the same manner except omitting the platinum reduction l I step was a solid melting at 100 C. NCO(OH,)3O7C C6Hu n When it was attempted to carry out the synthesis of H H the lsomerlc di-tertlary compound using 2,4-d1-tertiary- 10 amylphenol, it was found that during the hydrogenation step cleavage took place at the ether linkage. methoxyacetanilide Compound 11 (VII H2 H2 1 l H m-Pentadecylphenoxyacetic acid (M.P. 103-5) is pre- NHC i 1'5 pared in the usual manner and hydrogenated as described above. The acid is treated with triethylamine, ethyl H chloroformate and 6amino-2,4-dichloro-3-methylphenol as described for Compound I.

1 Compound III OCOCHOONH 2,4-di-n-amylphenol is treated with 'y-chlorobutyroni- 1 H trile and sodium hydroxide yielding 'y-(2,4-di-n-amyla henoxy)butyr0nitrile. The latter is hydrogenated to the figlfggigggfifgg corresponding diamylcyclohexyloxybutylamine which reacts readily with phenyl l-hydroxy-Z-naphthoate.

ILF O 02H Compound IV I NHCO The compound is prepared as described for Compound Hz Hz 1 l H l 0 CHO C5Hn-IJ I N H I except using the amine 1-(2,4,6-tr1chlorophenyl)-3 H (m-aminobenzamido)-5-pyrazolone prepared as described 0 Cl Hlrn in the Loria et al. U.S. Patent 2,600,788, granted June 17, 1952, in place of 6amino-2,4-dichloro-3-methylphe- 1-(2,4,6-trlchlorophenyD-3-[3-a-(2,4 -dl n amylcyclohexyloxy)-nutyramldo]benzamldo-5-pyrazolone The n-alkylcyclohexyloxy substituted couplers of the invention can be prepared as described below.

Compound V This compound is prepared as Compound IV was ex cept using the amine 1-(2,4,5-trichlorophenyl)-3-(maminobenzamido)-5-pyrazolone.

Compound VI Compound I 40 This compound is prepared in the manner of Com- NaOH PtOz n-C H1r OH CICHaCOOH ---b 11-051111 OCHgCOOH Odin-n I Calla-n CHrCH; (C H) N g ciobdene nC|H -C /CH-O CEBU 0 OH Compound I CHg-CH u-n 01 NH;

2,4-di-n-amylphenol is prepared by acylation of 'p-namylphenol (Sandulesco and Girard, Bull. soc. chim., 47, 1300 (1930)), with valeric acid (cf. McLamore, J. I 7 Cheme 73, 2221 (1 1)), f llowed by catalytic No. 575,099, filed March 30, 1956. The compound had hydrogenation s g pp chromite as ec y The a melting point of 57 (2. compared to 83 c. for the y P Y acid, formed y well-known n-diamylphenoxy analogue prepared in the same manner methods, is treated in acetic acid with hydrogen at 500- except omitting the platinum hydrogenation Step 1000 p.s.i. in the presence of Adams catalyst (PtO The 2,4-di-n-amylcyclohexyloxyacetic' acid is a liquid, Compound VII distilling at 161 at 0.2 mm., n 1.4655.

A solution of the foregoing acid in dioxane is treated with equimolar amounts of triethylamine and ethyl chloroformate at 10 for /2 hour. An equivalent amount 'y'butymlacmne' stirring continued for 16 hours water is added and amine a-(m-aminobenzoyl)-2-rnethoxyacetanilide.

the dark oil which separates is triturated several times with water. Trituration of the residual oil with hexane leavesa solid which is discarded. The hexane solution compound made in the same manner except omlttlng the is concentrated and distilled giving Compound'Yas-a 7 bydrogenation'step.

pound I except using as the amine a-(m-aminobenzoyly' Z-methoxyacetanilide prepared as described in Example 4 of the McCrossen et al. U.S. patent application Serial.

.'y-(p-n-Amylphenoxy)butyric acid is prepared by the; reaction of the sodium salt of p-n-amylphenol with; The acid is hydrogenated as forv Com-.

of 6 wozmdichloma methylphenol is added and pound I above and the product caused to react with the Compound VII had a melting point of 106 C. com-j pared to 147 C. for the analogous p-n-amylphenoxy- Compound VIII This compound (M.P. 128) is prepared in the manner of Compound I except using the amine a-benzoyl- 5-amino-2-methoxyacetanilide (McCrossen et al. invention above) and the hydrogenated acid prepared by reducing 'y-(2,4-di-n-amylphenoxy) butyric acid.

Compound IX Dissolution temperature C.)

Coupler VII analog 115 As mentioned, the lower dissolution temperature of the couplers of the invention prevents degradation of the couplers during incorporation in photographic emulsons.

The coupler compounds of the invention may be incorporated in sensitive silver halide emulsion layers as described in Mannes and Godowsky US. Patent 2,304,940 or Jelley and Vittum US. Patent 2,322,027. In a typical procedure, a suitable quantity of the coupler is dissolved in di-n-butylphthalate by heating and stirring. This solution is then mixed with a percent gelatin solution containing a dispersing agent and this passed through a colloid mill several times to disperse the coupler well. The dispersion may then be mixed with a suitable quantity of gelatino silver halide emulsion and coated in the normal manner on a film base.

The aromatic amino developing agents used with the coupler compounds of our invention include the mono-, diand tri-amino aryl compounds and their derivatives formed by substitution in the amino group as well as in the ring such as alkyl phenylene diamines and alkyl toluylene diamines. These compounds are usually used in the salt form such as the hydrochloride or the sulfate which are more stable than the amines themselves. Suitable compounds are di-ethyl-p-phenylene diamine hydrochloride, monoethyl-p-phenylene diamine hydrochloride,

di-methyl-p-phenylene diamine hydrochloride, di-methylp-phenylene sulfate and 2-amino-5-di-ethyl amino toluene sulfate. The p-amino phenols and their substitution products may also be used where the amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color-forming compounds to form a dye image.

The following is a color developing solution which may be used to develop colored images in emulsion layers containing the coupler compounds of the invention:

p-Aminodiethylaniline sulfate grams 2 Sodium sulfite (anhydrous) do 5 Sodium carbonate (anhydrous) do 20 Potassium bromide do 2 Water to liter 1 The colloid vehicle of the emulsions containing the coupler compounds of the invention may be gelatin or other carriers such as collodion, organic esters of cellulose or synthetic resins. The support for the emulsion may be a transparent material such as glass, cellulose ester or a non-transparent reflecting material such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or as superposed layers on one or both sides of the support. The superposed layers may be diiferentially sensitized to form natural color photographic images in the well-known manner. For example, in a multilayer material sensitized to red, green and blue light, respectively, our couplers would ordinarily be used in the green-sensitive emulsion layer to form the magenta image.

What we claim is:

A photographic silver halide emulsion containing the coupler compound 6-[a-(3-n-pentadecylcyclohexyloxy)- acetamido] -2,4-dichloro-3-methylphenol.

References Cited in the file of this patent UNITED STATES PATENTS 2,280,722 Schneider Apr. 21, 1942 2,423,730 Salminen et al. July 8, 1947 2,474,293 Weissberger et al. June 28, 1949 2,589,004 Weissberger et al. Mar. 11, 1952 2,618,641 Weissberger ct al. Nov. 18, 1952 2,704,711 Hanson Mar. 22, 1955 OTHER REFERENCES Handbook of Chem. & Physics, pp. 752, 753, 764, 765, 970, 971. The 30th ed. (1947), Chem. Rubber Publ. (30., Cleveland, Ohio. 

